Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/22—Organic compounds containing nitrogen
  • C10L1/232—Organic compounds containing nitrogen containing nitrogen in a heterocyclic ring
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
  • C10L1/2443—Organic compounds containing sulfur, selenium and/or tellurium heterocyclic compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M133/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen
  • C10M133/02—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing nitrogen having a carbon chain of less than 30 atoms
  • C10M133/38—Heterocyclic nitrogen compounds
  • C10M133/44—Five-membered ring containing nitrogen and carbon only
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M135/00—Lubricating compositions characterised by the additive being an organic non-macromolecular compound containing sulfur, selenium or tellurium
  • C10M135/32—Heterocyclic sulfur, selenium or tellurium compounds
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
  • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
  • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
  • H01B3/20—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances liquids, e.g. oils
  • H01B3/22—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances liquids, e.g. oils hydrocarbons
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/22—Heterocyclic nitrogen compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/22—Heterocyclic nitrogen compounds
  • C10M2215/221—Six-membered rings containing nitrogen and carbon only
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/22—Heterocyclic nitrogen compounds
  • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/22—Heterocyclic nitrogen compounds
  • C10M2215/225—Heterocyclic nitrogen compounds the rings containing both nitrogen and oxygen
  • C10M2215/226—Morpholines
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2215/00—Organic non-macromolecular compounds containing nitrogen as ingredients in lubricant compositions
  • C10M2215/30—Heterocyclic compounds
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
  • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
  • C10M2219/09—Heterocyclic compounds containing no sulfur, selenium or tellurium compounds in the ring
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/14—Electric or magnetic purposes
  • C10N2040/16—Dielectric; Insulating oil or insulators
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
  • C10N2040/00—Specified use or application for which the lubricating composition is intended
  • C10N2040/14—Electric or magnetic purposes
  • C10N2040/17—Electric or magnetic purposes for electric contacts

Definitions

• This invention relates to hydrocarbon compositions containing selected heteroaromatic nitrogen compounds as antioxidant/metal deactivators/ electrical insulators and particularly to lubricant and speciality oil compositions such as electrical insulating oils containing such compounds.
• antioxidant/metal deactivators in hydrocarbon compositions such as lubricants and speciality oils and in other applications has been widespread for a good many years.
• Some of the representative types of antioxidants used in lubricating oils are noted in "Lubricant Additives" by C. V. Smalheer and R. K. Smith, 1967, pp. 7, including hindered phenols such as 2,6-ditertiary- butyl-4-methyl phenol and amines such as N-phenyl alpha naphthylamine.
• U.S. Patent 1,768,910 discloses the use of compounds such as pyridine, quinoline and piperidine;
• U.S. Patent 2,136,788 disloses the use of quinaldine;
• U.S. Patent 2,377,423 discloses the product of a diene and an aromatic amine such as 1,3 butadiene and p,p' diamino diphenyl methane;
• U.S. Patent 2,647,824 discloses the combination of a hydrogenated quinoline and an amino phenol;
• U.S. Patent 3,190,835 discloses a disubstituted isoindoline compound; a variety of benzotriazole compounds are disclosed in U.S.
• antioxidant/metal deactivator-type compounds that are available, there is always the need and desire to find additional compounds having improved properties particularly ones that have antioxidant/ metal deactivator properties as well as good electrical insulating properties and are especially useful in speciality-type applications such as electrical insulating oils.
• heteroaromatic nitrogen compounds such as purine are particularly useful as antioxidants/metal deactivators/electrical insulators in hydrocarbon compositions and especially lubricating and speciality oil compositions such as electrical insulating oils.
• This invention is directed to the use of selected heteroaromatic nitrogen compounds as antioxidant/metal deactivators/electrical insulators in hydrocarbon compositions. More particularly, the selected antioxidant/metal deactivator/electrical insulator compounds of this invention are of a type having the following general formula: wherein each X is CH, C-alkyl or N with at least one X being N; Y is CH, C-alkyl or N; R is H or CH2NR2' where each R" is H or alkyl of 1 to 20 carbons; R' is H, SR"', OR"' or NR 2 "' where each R"' is H or alkyl of 1 to 20 carbons.
• both X groups will be N, Y will be CH, or C-alkyl and the alkyl groups in R" and R'" will contain 8 to 16 carbon atoms.
• Additonal substituent groups for example, alkyl groups, may be added to other places on the ring structure (I) and other types of substituents besides those noted above may also be used to provide such compounds (I) with the desired oil solubility.
• Illustrative compounds of the type identified by the general formula (1) include purine, 6-aminopurine, 4-azabenzimidazole, 8-azaadenine, 6-octylthiopurine, 6-decylthiopurine, 9-diethy- laminomethylpurine, 9-dibutyi-aminomethyi- purine, 9-dioctylaminomethylpurine and 9-di- dodecylaminomethylpurine. Particularly preferred is purine and derivatives thereof.
• the antioxidant/metal deactivators/electrical insulators defined by general formula (I) may be used in any hydrocarbon composition as the base composition and more particularly in lubricating and speciality oils and petroleum fuels.
• the base compositions which may utilize the antioxidant/metal deactivators/electrical insulators (I) are conventional hydrocarbon oils of lubricating viscosity including mineral or synthetic lubricating oils.
• the lubricating oils employed may be of any suitable lubricating viscosity and may range from about 30 to about 7,500 SUS at 37.8°C (100F°).
• Particularly useful as the base compositions in this invention are lubricating and speciality oils, preferably electrical insulating oils such as transformer oils which have relatively low viscosity values and more particularly a viscosity of 40 to 100 SUS at 37.8°C (100F°).
• the fuel compositions which are useful as base compositions include petroleum distillate fuels and oils and are not restricted to straight-run fuels and oils but can comprise straight-run distillates, catalytically or thermally cracked distillate fuels or mixtures of staight-run distillate fuel oils, naphthas and the like, with cracked distillate fuels. Moreover, such fuels and oils can be treated in accordance with well known commercial methods such as acid or caustic treatment, hydrogenation, solvent refining, clay treatment, etc.
• fuels and fuel oils are those boiling in the gasoline range, jet fuels, domestic fuel oils such as No. 1, 2 and 3 fuel oils used in heating and as diesel fuel oils and turbine fuels.
• domestic fuel oils generally conform to the specifications set forth in ASTM Specification D396-48T.
• Specifications for diesel fuels are defined in ASTM Specification D975-48T.
• Typical jet fuels are defined in Military Specification MIL-F-5624B.
• the preferred base or basestock compositions are the mineral oils and more particularly those of lubricating viscosity, especially those useful as lubricating and speciality oils such as electrical insulating oils. Further description of lubricating oils useful as the base composition may be found in Kirk-Othmer, Encyclopedia of Chemical Technology, 2nd Edition Vol. 12, 1967, pp 557 to 616.
• the base hydrocarbon composition will make up a major portion by weight of the compositions of this invention with the antioxidant/metal deactivator/electrical insulator comprising an effective inhibitive amount. More particularly, the antioxidant/metal deactivator/electrical insulator will comprise from about 0.0001 to about 1.0 percent by weight and preferably from about 0.001 to about 0.05 percent by weight, based on the total weight of the composition.
• antioxidant/metal deactivator/electrical insulator (I) may also be added to the hydrocarbon base composition containing the antioxidant/metal deactivator/electrical insulator (I) in accordance with this invention depending on the particular application of said composition.
• Such additives include dispersants, extreme pressure additives, pour point depressants and also other known antioxidants such as 2,6-ditertiary butyl para cresol. Additional disclosures of useful additives may be found in "Lubricant Additives" by C. Smalheer et al. described above.
• a refined electrical insulating oil which was essentially a mineral oil having a viscosity of 58 SUS at 100°F was formulated with 0.06 weight percent of 2,6-ditertiary butyl para cresol. Using the Rotating Bomb Test (ASTM D-2112) its life was found to be 109 minutes. Sludge formation and soluble acidity buildup was also determined using the D-2440 oxidation test (164 hrs.). The same electrical insulating oil but containing 0.01 % by weight of purine was also tested for life using the Rotating Bomb Test (ASTM D-2112) and showed a significant increase in life to 190 minutes. Carrying out the D-2440 oxidation test for this oil containing purine, a significant retardation of sludge formation and soluble acidity buildup was demonstrated.
• An electrical insulating oil of the same composition as in Example I containing 0.3 percent by weight of 2,6-ditertiary butyl para cresol was formulated with 0.054% of 6-aminopurine.
• This composition showed a signification reduction of 62% in the depletion of phenol component (compared with the composition without the aminopurine) in the first day of a copper catalyzed oxidation test. This test was run in accordance with ASTM D2440 conditions except at 120°C.
• An electrical insulating oil of the same composition as Example I was formulated with 0.06 wt. % of 2,6-ditertiary butyl para cresol and 0.015 wt. % of 4, 5, 6, 7 tetrahydrobenzotriazole (formerly sold commercially by Ciba-Geigy as Reomet SBT). Carrying out the D-2440 oxidation test (164 hours), results indicated 0.16 wt. % sludge and an acid number of 1.70 mg KOH/g. In comparison the base electrical insulating oil without the benzotriazole compounds gave a sludge weight of 0.85% and acid number of 3.45.
• a refined electrical insulating oil as in Example I was formulated with 0.06 weight percent of 2,6- ditertiary butyl para cresol. Testing on the Rotating Bomb test (ASTM D-2112) showed its life to be 196 minutes.
• An electrical insulating oil as in Example I containing 0.06 wt. % of 2,6-ditertiary butyl para cresol and 0.07 wt. % of a pour point depressant which was a chlorinated wax/naphthalene condensation product dissolved in solvent mineral oil and having a chlorine content of about 0.5 wt. % or less was formulated and tested for oxidation usig the ASTM D-2440 (24 hour) test which showed moderate sludge formation, an acid number of 1.46 mg KOH/g and an interfacial tension of 10.4 (mN/m).
• the 164 hr. ASTM D-2440 test showed a 0.8 wt. % sludge and 3.46 acid number.
• Example V The same formulation as in Example V was tested using 0.0025 wt. % of 9-dibuty- laminomethylpurine instead of the octylthiopurine, with the following results.
• Example V An electrical insulating oil as in Example V containing 0.08 wt. % of the 2, 6-ditertiary butyl para cresol and 0.07 wt. % of the chlorinated wax/ naphthalene pour point depressant was formulated and tested for oxidation using the ASTM D-2440 (164 hr.) test which showed a 0.39 wt. % sludge and 2.10 acid number.
• Example VII The same formulation as in Example VII was tested using 0.005 wt. % of 9-didodecyl- aminomethylpurine.
• the D-2440 oxidation test (164 hours) resulted in 0.01 wt. % sludge and an acid number of 0.04.
• the oil to be tested was a refined electrical insulating oil which was essentially a mineral oil having a viscosity of 8.68 cSt at 40°C containing 0.06 wt. % of of 2, 6-ditertiary butyl para cresol and 0.07 wt. % of the chlorinated wax/naphthalene pour point depressant described in Example V.
• the 60 Hz test was conducted by applying a voltage approximately 30% below the expected breakdown for one minute. If no breakdown occurred, the voltage was increased by 5% and again held for one minute. The procedure was repeated until breakdown occurred. Ten breakdowns were observed using fresh oil charges each time with the resulting means breakdown voltage of 43.6 kV (standard deviation 6.9).
• a switching surge test was conducted on the same test oils by applying a surge voltage with a rise time of 200 microseconds and a tail length of 1,000 microseconds.
• the first voltage application was at approximately 30% below the expected breakdown voltage. If no breakdown occurred, the voltage was applied three times at that level and then increased by 5%. This procedure was repeated until breakdown occurred with the peak value of the surge voltage that produced breakdown recorded. Ten breakdowns were observed using fresh oil each time with the resulting mean breakdown voltage of 50.9 kV (std. deviation 8.6).
• Oxidation properties for the two oils were also determined using the ASTM D-2440 (164 hour) test with the oil alone giving 0.76 wt. % sludge and an acid number of 3.07 and the oil containing purine giving a 0.01 wt. % sludge and an acid number of nil.
• results disclosed in the several examples above show the particularly desirable oxidation properties of the compounds of the type defined by formula (I) and also show the desirable electrical insulating properties of such compounds when added to hydrocarbon compositions such as mineral oils.

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• Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Physics & Mathematics (AREA)
• Spectroscopy & Molecular Physics (AREA)
• Lubricants (AREA)
• Organic Insulating Materials (AREA)
• Liquid Carbonaceous Fuels (AREA)
• Anti-Oxidant Or Stabilizer Compositions (AREA)

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• 1981
  • 1981-07-02 US US06/280,073 patent/US4367152A/en not_active Expired - Lifetime
• 1982
  • 1982-06-23 EP EP82303269A patent/EP0069507B1/en not_active Expired
  • 1982-06-23 DE DE8282303269T patent/DE3273166D1/de not_active Expired
  • 1982-06-30 CA CA000406338A patent/CA1172237A/en not_active Expired
  • 1982-07-01 NO NO822311A patent/NO157425C/no unknown
  • 1982-07-01 JP JP57112624A patent/JPS5823892A/ja active Pending

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